1-(2,6-diisopropylphenyl)-3-methyl imidazolium iodide | 852057-21-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-(2,6-diisopropylphenyl)-3-methyl imidazolium iodide
• 英文别名: 1-(2,6-diisopropylphenyl)-3-methylimidazolium iodide；MeIiPr*HI
• CAS: 852057-21-7
• 化学式: C₁₆H₂₃N₂*I
• 分子量: 370.277
• InChiKey: ZWAORKUULNECEV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.55
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  8.81
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(2,6-diisopropylphenyl)-3-methyl imidazolium iodide 在 silver(l) oxide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  铁催化的芳基镁试剂与芳基氯化物和甲苯磺酸盐的交叉偶联反应：配体结构参数的影响和一般N-杂环碳烯配体的鉴定

  摘要：

  对芳基氯化物与芳基镁试剂的铁催化的交叉偶联反应中的N-杂环卡宾配体进行了系统的评估。N-杂环卡宾的供体强度与反应结果之间没有明确的相关性。取而代之的是，具有高％V bur值的对空间要求高的配体获得了期望的联芳基产物的最高产率。通过这项研究，SIPrNap已被确定为芳基氯化物和甲苯磺酸盐偶联的有效且通用的配体。

  DOI：

  10.1021/acs.organomet.7b00180
• 作为产物：
  描述：

  1-(2,6-二异丙基苯基)-1H-咪唑 、 碘甲烷 以 二氯甲烷 为溶剂， 反应 16.0h， 以98%的产率得到1-(2,6-diisopropylphenyl)-3-methyl imidazolium iodide
  参考文献：
  名称：

  Allylic alkylation and amination using mixed (NHC)(phosphine) palladium complexes under biphasic conditions

  摘要：

  A dramatic improvement of the catalytic activity was observed when a phosphine was added in allylic alkylation reactions catalyzed by (NHC)Pd(eta(3)-C3H5)Cl complexes. Consequently, several palladium complexes, generated in situ from different NHC-silver complexes, [Pd(eta 3-C3H(5))Cl](2) and PPh3, were tested in this reaction to evaluate their potential. High reaction rates and conversions could be obtained with this catalytic system in the alkylation of allylic acetates with dimethylmalonate, particularly under biphasic conditions using water/dichloromethane and KOH 1 M as the base. These conditions are experimentally more convenient and gave higher reaction rates than the classical anhydrous conditions (NaH/THF). In this system, the phosphine is essential since no conversion was obtained when it is not present. The steric hindrance of the carbene ligand has a great influence on the activity and the stability of the catalytic system. The best NHC ligands for this reaction are either 1-mesityl-3-methyl-imidazol-2-ylidene or 1-(2,6-diisopropylphenyl)-3-methylimidazol- 2-ylidene which are less bulky among the NHC tested. These two ligands led in 5 min to a complete conversion at 20 degrees C. The Pd-catalyzed allylic amination reaction using (E)-1,3-diphenylprop-3-en-yl acetate and benzylamine was also tested with (NHC)(PPh3)Pd complexes and under the biphasic conditions. This reaction was found to be slower than the alkylation with dimethylmalonate but a ;complete conversion could be reached in 6 h at 20 degrees C using K2CO3 1 M as the base. NMR experiments indicated that mixed (NHC)(PPh3) Pd complexes are formed in situ but their structure could not be established exactly. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.10.012
• 作为试剂：
  描述：

  二对甲苯基硼酸 、 对氯苯乙酮 在 1-(2,6-diisopropylphenyl)-3-methyl imidazolium iodide 、 potassium phosphate monohydrate 、 trans-chloro(phenyl)bis(triphenylphosphine)nickel(II) 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以63%的产率得到4-乙酰基-4'-甲基联苯
  参考文献：
  名称：

  O，N螯合的二芳基硼酸酯与芳基氯化物和甲磺酸酯的 镍催化交叉偶联†

  摘要：

  一种实用的镍催化剂体系，由容易获得的反式-NiCl（Ph）（PPh 3）2 / [Iprmim] I / K 3 PO 4 ·3H 2组成。已经开发出甲苯中的O，以使3-二甲基氨基丙基二芳基硼酸酯与芳基氯化物和甲磺酸酯有效地交叉偶联。已经发现少量的水对于实现系统的高效率至关重要。如对照实验所示，在不仅与二芳基硼酸酯而且二芳基硼酸，芳基硼酸，酸酐和三氟硼酸酯交叉偶联中，镍催化剂体系对芳基氯化物和甲磺酸酯的活性比相应的甲苯磺酸酯显着更高。通过使用3–5％mol％的镍催化剂，可以以优异的收率获得各种电子形式的联芳基，而位阻受阻的联芳基的收率则相对较低。

  DOI：

  10.1039/c8nj05503c

文献信息

• On the Dual Role of N-Heterocyclic Carbenes as Bases and Nucleophiles in Reactions with Organic Halides
  作者：Axel Jacobi von Wangelin、Christiane Knappke、Anthony Arduengo, III、Haijun Jiao、Jörg-Martin Neudörfl

  DOI：10.1055/s-0031-1289593

  日期：2011.12

  nucleophilicities, and sterics of N-heterocyclic carbenes have been studied in reactions of imidazolin-2-ylidenes with organic halides. Highly nucleophilic and less basic carbenes cleanly gave alkyli­deneimidazolines, the deoxy analogues of Breslow-type intermediates. More basic NHCs engaged in unwanted deprotonation or dehydrohalogenation reactions. N-heterocyclic carbenes - enamines - umpolung - imidazoles - nucleophilicity

  已在咪唑啉-2-亚烷基与有机卤化物的反应中研究了N-杂环卡宾的不同碱性，亲核性和空间位阻的合成结果。高度亲核性和碱性较低的卡宾可以干净地得到亚烷基亚咪唑啉，这是Breslow型中间体的脱氧类似物。更多的碱性NHC参与不需要的质子化或脱氢卤化反应。 N-杂环卡宾-烯胺-乌泊隆-咪唑-亲核性
• Allylic Amination Using Well‐Defined [(NHC)Pd(η ³ ‐allyl)Cl] Complexes and PPh ₃
  作者：Sylvain Roland、William Cotet、Pierre Mangeney

  DOI：10.1002/ejic.200801157

  日期：2009.5

  at the allyl fragment. This reaction occurs exclusively in the presence of PPh3, thus suggesting that cationic [(NHC)Pd(allyl)(PPh3)]+ complexes, which are more electrophilic, are formed in situ and allow the amine to react with the allyl fragment. A tetrafluoroborate cationic complex has therefore been prepared from [(NHC)Pd(allyl)Cl], PPh3, and AgBF4 and fully characterized. This complex is an active

  研究了 [(NHC)Pd(allyl)Cl] 配合物催化的烯丙基胺化反应，发现 PPh3 的存在对于催化体系的活性至关重要。 [(1-Mesityl-3-methylimidazol-2- ylidene)Pd(η3-C3H5)Cl] 已用于优化与 (E)-1,3-diphenylprop-3-enyl 乙酸酯和苄胺在双相条件（碱水/CH2Cl2）下的反应条件。使用 1 M K2CO3 水溶液获得分离产物的最佳产率 (98%)。还检查了 NHC 配体和烯丙基片段对预催化剂的影响。两种新的中性 [(NHC)Pd(η3-1-RC3H4)Cl] 配合物 [NHC = 1-mesityl-3-methylimidazol-2-ylidene or 1-(2,6-diisopropylphenyl)-3-methylimidazol-2-ylidene ; R = H 或 Ph] 已制备，使用前者观察到反应时间减少。NMR
• Steric Effects in the Aerobic Oxidation of π-Allylnickel(II) Complexes with <i>N</i>-Heterocyclic Carbenes
  作者：Benjamin R. Dible、Matthew S. Sigman

  DOI：10.1021/ic0612451

  日期：2006.10.1

  Pi-allylchloro(NHC)nickel(II) complexes were synthesized and their reactions with O2 were studied. Ligand steric effects were found to determine the difference between rapid oxidation of the allyl group to produce bis-mu-hydroxonickel complexes and no observable reaction. The ability of the metal-NHC bond to rotate correlates with the ability of the complex to react with O2. In the limiting cases,

  合成了对烯丙基氯（NHC）镍（II）配合物，并研究了其与O2的反应。发现配体的空间效应确定了烯丙基的快速氧化以产生双-mu-羟基酮络合物与没有可观察到的反应之间的差异。金属-NHC键旋转的能力与配合物与O2反应的能力相关。在极限情况下，构象受限的配合物对O2稳定，且Ni-NHC键快速旋转的配合物与O2迅速反应。发现具有中间构象柔韧性的复合物与O 2的反应性较低。基于观察到的鞍形配体对O2的配合物的惰性，我们建议在与O2反应时采用非平面几何形状。
• Hydrogen bonding-enabled gold catalysis: ligand effects in gold-catalyzed cycloisomerizations in hexafluoroisopropanol (HFIP)
  作者：Nikolaos V. Tzouras、Alberto Gobbo、Nestor Bracho Pozsoni、Savvas G. Chalkidis、Subhrajyoti Bhandary、Kristof Van Hecke、Georgios C. Vougioukalakis、Steven P. Nolan

  DOI：10.1039/d2cc03056j

  日期：——

  Gold catalysis has witnessed immense evolution in recent years, yet it still requires the use of activators to render the common [AuCl(L)] complexes catalytically active. Herein, the H-bonding donor properties of hexafluoroisopropanol (HFIP) are utilized for Au–Cl bond activation and the ancillary ligand and counteranion effects on cycloisomerization reactions are showcased in HFIP as solvent.

  金催化近年来经历了巨大的发展，但它仍然需要使用活化剂来使常见的 [AuCl(L)] 配合物具有催化活性。在此，六氟异丙醇（HFIP）的氢键供体特性用于Au-Cl键活化，辅助配体和抗衡阴离子对环异构化反应的影响在HFIP作为溶剂中得到展示。
• Piano‐Stool Ruthenium <i>N</i>‐Heterocyclic Carbene Complexes for <i>gem</i>‐Specific Catalytic Dimerization of Terminal Alkynes
  作者：Kasumi Hayashi、Qiuming Liang、Franka Philippi、Datong Song

  DOI：10.1002/ejic.202300168

  日期：2023.7.25

  A series of piano-stool Ru-NHC (NHC=N-heterocyclic carbene) complexes with various levels of steric congestion have been used as precatalysts in the catalytic dimerization of terminal alkynes. The most congested complexes of this series give 100 % gem-enyne products at ambient temperature when activated with a base.

  一系列具有不同空间拥挤程度的钢琴凳Ru-NHC（NHC= N-杂环卡宾）配合物已被用作末端炔烃催化二聚反应的预催化剂。当用碱激活时，该系列中最稠密的配合物在环境温度下可产生 100%宝石-烯炔产品。